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    • 专利摘要:
    The present invention relates to an electrically conductive composition comprising a dispersant and a radiation curable resin of the electrically conductive particles in the dispersant, wherein the dispersant of the electrically conductive particles comprises a binder and an electrically conductive polymer and is stabilized by a nonionic stabilizer. The present invention also relates to the use of the composition for use in conductive coatings, to coatings prepared using the compositions according to the invention and to substrates coated in whole or in part with the coatings.
    公开号:KR20000070078A
    申请号:KR1019997006299
    申请日:1998-01-07
    公开日:2000-11-25
    发明作者:잔센죠한프란츠그라두스안토니우스
    申请人:윌리암 로엘프 드 보에르；디에스엠 엔.브이；
    IPC主号:
    专利说明:

    Radiation curable conductive coating dispersant, method for manufacturing same and coating material made therefrom {RADIATION CURABLE CONDUCTIVE COATING DISPERSION, PROCESS FOR ITS PREPARATION AND COATINGS MADE OF IT}
    The present invention relates to an electrically conductive composition consisting of a dispersant of a radiation curable resin and electrically conductive particles in a dispersant.
    Such compositions are known from EP 591,951. EP 591,951 describes an electrically conductive composition consisting of a dispersant of a radiation curable resin and polyaniline particles in an organic solvent.
    A drawback of the known compositions is that the electrically conductive coatings thus made increase turbidity as the electrical conductivity is improved.
    It is an object of the present invention to provide a composition which does not exhibit the above drawbacks.
    This object is achieved according to the invention by the dispersant of the electrically conductive particles comprising a binder and an electrically conductive polymer and stabilized by a nonionic stabilizer.
    The radiation curable resin preferably comprises the following components: (a) a compound having an ethylenically unsaturated group on the electron-sponsorable group, (b) a compound having an ethylenically unsaturated group on the electron-donating group Or non-combined, or (c) an allyl group-containing compound on an electron-donating group, or a mixture of compounds (b) and (c).
    The ethylenically unsaturated group (a) on the electron-withdrawing group is characterized by the following formula (1).
    X may be, for example, one of the following groups: OR 4 , NR 4 R 5 , SR 4 . R 1 , R 2 , R 3 may be, for example, the following groups: H, C 1 -C 20 alkyl, aryl, substituted aryl, COOR 6 , CONR 6 R 7 , CH 2 COOR 6 , CH 2 OR 6 , OR 6 , NR 6 R 7 , SR 6 , Cl or CN. Wherein R 4 , R 5 , R 6 and R 7 may be selected from the following groups: H, C 1 -C 20 , alkyl (including linear or cyclic structures), aryl, substituted aryl, O -Heterocycles containing S-, N- or P-atoms, aromatic heterocycles containing O-, S-, N- or P-atoms, COY, CH 2 COY, CH 2 OY, CH 2 NYZ, 2CH 2 SY, CH 2 CH 2 OY, CH 2 CH 2 NYZ, CH 2 CH 2 SY, CH 2 CH (CH 3 ) OY, CH 2 CH (CH 3 ) NYZ, CH 2 CH (CH 3 ) SY, CH (CH 3 ) CH 2 OY, CH (CH 3 ) CH 2 NYZ, CH (CH 3 ) CH 2 SY, (CH 2 O) n Y, (CH 2 NZ) n Y, (CH 2 S) n Y, (CH 2 CH 2 O) n Y, (CH 2 CH 2 NZ) n Y, (CH 2 CH 2 S) n Y, (CH 2 CH (CH 3 ) O) n Y, (CH 2 CH (CH 3 ) NZ) n Y, (CH 2 CH (CH 3 ) S) n Y, (CH (CH 3 ) CH 2 O) n Y, (CH (CH 3 ) CH 2 NZ) n Y, (CH (CH 3 ) CH 2 S) n Y. n is a number between 1-100 and Y and Z may be selected from the following groups: H, C 1 -C 20 alkyl (including linear or cyclic structures), Aryl, substituted aryl, heterocycle including O-, S-, N- or P-atoms, O-, S-, N- or P- Aromatic heterocycles containing atoms. As derivatives of these compounds, for example esters, urethanes, ureas, thiourethanes and anhydrides can also be used.
    Preferably the following compounds or combinations thereof are used: acrylate (X = OR 4 , R 1 = H, R 2 = H, R 3 = H), methacrylate (X = OR 4 , R 1 = CH 3 , R 2 = H, R 3 = H), acrylamide (X = NR 4 R 5 , R 1 = H, R 2 = H, R 3 = H), fumarate (X = OR 4 , R 1 = H , R 2 = COOR 6 , R 3 = H), malate (X = OR 4 , R 1 = H, R 2 = H, R 3 = COOR 6 ), itaconate (X = OR 4 , R 1 = CH 2 COOR 6 , R 2 = H, R 3 = H), citraconate (X = OR 4 , R 1 = CH 3 , R 2 = H, R 3 = COOR 6 ), or mesaconate (X = OR 4 , R 1 = CH 3 , R 2 = COOR 6 , R 3 = H) and derivatives thereof including for example fumaramide-ester, maleamide-ester and fumaramide. Cyclic structures in which X can be bonded to R 1 , R 2 or R 3 can also be used. An example of such a cyclic structure is maleimide, which may be characterized by the following formula (2):
    Wherein R 4 may be selected from the following groups: H, C 1 -C 20 alkyl (including linear or cyclic structures), aryl, substituted aryl, O-, S-, N- or P- Heterocycles containing atoms, aromatic heterocycles containing O-, S-, N- or P-atoms, COY, CH 2 COY, CH 2 OY, CH 2 NYZ, 2CH 2 SY, CH 2 CH 2 OY, CH 2 CH 2 NYZ, CH 2 CH 2 SY, CH 2 CH (CH 3 ) OY, CH 2 CH (CH 3 ) NYZ, CH 2 CH (CH 3 ) SY, CH (CH 3 ) CH 2 OY, CH ( CH 3 ) CH 2 NYZ, CH (CH 3 ) CH 2 SY, (CH 2 O) n Y, (CH 2 NZ) n Y, (CH 2 S) n Y, (CH 2 CH 2 O) n Y, (CH 2 CH 2 NZ) n Y, (CH 2 CH 2 S) n Y, (CH 2 CH (CH 3 ) O) n Y, (CH 2 CH (CH 3 ) NZ) n Y, (CH 2 CH (CH 3 ) S) n Y, (CH (CH 3 ) CH 2 O) n Y, (CH (CH 3 ) CH 2 NZ) n Y, (CH (CH 3 ) CH 2 S) n Y.n is Number between 1-100 and Y and Z may be selected from the following groups: H, C 1 -C 20 alkyl (including linear or cyclic structures), aryl, substituted aryl, O-, S Heterocycles containing N- or P-atoms, including O-, S-, N- or P-atoms Aromatic heterocycles. As derivatives of these compounds, for example esters, urethanes, ureas, thiourethanes and anhydrides can also be used.
    Compound (b) having an ethylenically unsaturated group on the electron-donating group is preferably vinyl ether, vinyl ester, vinyl amide, vinylamine, vinyl thioether or vinyl thioester. Derivatives of the above may also be used.
    The allyl group-containing compound (c) on the electron-donating group is preferably allyl ether, allyl ester, allyl alcohol, allyl amine or allyl amide. Such derivatives may also be used.
    The amount of ethylenically unsaturated groups (a) on the electron-withdrawing groups of the radiation curable resin is usually between 25% and 100%. The amount of the ethylenically unsaturated group (b) on the electron-donating group or the mixture of the (b + c) of the allyl group-containing compound or the radiation curable resin on the electron-donating group is the electron-susceptibility of the radiation-curing resin. Between 0% and 75% depending on the amount of ethylenically unsaturated groups (a) on the group.
    According to a preferred embodiment, the radiation curable resin comprises all of compound (a) having an ethylenically unsaturated group on the electron-withdrawing group, or a compound having 50 mol% of compound (a) and an ethylenically unsaturated group on the electron-donating group (b) 50 mol%, or an allyl group-containing compound (c) or a mixture of (b) and (c). The mol% mentioned here refer to radiation cured ethylenically unsaturated groups. Compound (a) having an ethylenically unsaturated group (a) has an acrylate, methacrylate, maleate, fumarate, itaconate, citraconate or mesaconate group.
    Compound (a) having an ethylenically unsaturated group on the electron-withdrawing group can be linked to the polymer or oligomer via R 4 . Examples of such polymers or oligomers are polyurethanes, polyesters, polyacrylates, polyethers, hydrocarbon polymers, for example polyolefins, polysilicates, polycarbonates, polyvinyl esters, cyclones containing ethene, propene, butadiene and styrene Rubbers such as (co) polymers of pentadiene, polyisoprene, natural rubber and polyepoxides. Mixed polymers are, for example, polyether urethanes, polyester urethanes, polyether carbonates and polyepoxide esters. Combinations of polymers or oligomers may also be used. R 4 is other than an e-ethylenically unsaturated group (a) are, for example COOR 6, CONR 6 R 7, CH 2 COOR 6 or CH 2 R as OR 6 1, R 2 or R 3 in the job sex group In the case of including additional functional groups in the form, the ethylenically unsaturated groups may be included in the polymer or oligomeric chain.
    Examples of such polymers or oligomers are unsaturated polyesters having fumarate, maleate, itaconate, citraconate or mesaconate functional groups that can be used in the synthesis of the polymer or oligomer.
    Preferably, the number of ethylenically unsaturated groups on the electron-withdrawing groups on the polymer or oligomer is greater than one.
    The ethylenically unsaturated group (b) on the electron-donating group or the allyl group-containing compound (c) on the electron-donating group can be linked to the polymer or oligomer described above via an ether, ester amine or amide compound. And in the case of bifunctional ethylenically unsaturated groups on the electron-donating group or on the bifunctional allyl compound, it may also be added to the polymer or oligomer chain.
    In addition to the ethylenically unsaturated groups described above on or in polymers or oligomers, the radiation curable resins may also comprise low molecular weight compounds having ethylenically unsaturated groups. Examples of the above include ethyl acrylate, methyl acrylate, propyl acrylate, ethyl methacrylate, methyl methacrylate, propyl methacrylate, hexane diol diacrylate, hexane diol dimethacrylate, trimethylolpropane triacrylate , Trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, acrylamide N-methylacrylamide, acrylamide, N-ethyl acrylamide, such as N-lauryl acrylamide, N-butyl acrylamide, N-octyl acrylamide, N, N-dimethyl acrylamide, N, N- diethyl acrylamide, ethyl maleate, diethyl mal Rate, Methyl Maleate, Dimethyl Maleate, Hexyl Maleate, Dihexyl Maleate, Cyclohexyl Male , Maleate esters such as dicyclohexyl maleate, octyl maleate, dioctyl maleate, N, N'-bismaleamide, N, N'-dimethylmaleamide, N, N'-diethyl maleamide, Maleamides such as N, N-diethylmaleamide, maleimide, N-methyl maleimide, maleimide such as N-hexyl maleimide, N-cyclohexyl maleimide, ethyl fumarate, diethyl fumarate, methyl fumar Latex, dimethyl fumarate, hexyl fumarate, dihexyl fumarate, cyclohexyl fumarate, dicyclohexyl fumarate, octyl fumarate, dioctyl fumarate, fumarate esters such as fumaramide, methyl itaconate, dimethyl itata Conate, Ethyl Itaconate, Diethyl Itaconate, Hexyl Itaconate, Dihexyl Itaconate, Cyclohexyl Itaconate, Dicyclohexyl Itaconate, Itacone Amide, Ita Itaconic acid esters such as cone imide, methyl citraconate, dimethyl citraconate, ethyl citraconate, citraconic acid ester such as diethyl citraconate, methyl mesaconate, dimethyl mesaconate, ethyl, mesaco Acrylates, mesaconic acid esters such as diethyl mesaconate, butylvinyl, ether cyclohexyl, dimethanol divinyl ether, butyldivinyl ether, triethylene glycol divinyl ether and hydroxybutylvinyl ether, allyl alcohol , Allyl ether, diallyl ether, allylamine, diallylamine, triallylamine, trimethylolpropane allyl ether, trimethylolpropane diallyl ether, trimethylolpropane triallyl ether, pentaerythritol allyl ether, pentaerythritol diallyl Ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether , An allyl ester compound such as allyl acetate, diallyl adipate esters, and diallyl phthalate ester.
    Depending on the radiation light source and the composition used to cure the resin, the radiation curable resin includes a photoinitiator. Examples of suitable photoinitiators are described, for example, in volume 3 van 'Chemistry and Technology of UV and EB Formulation' door K Dietliker (1992; SITA Technology Ltd. London).
    Dispersants of the electrically conductive particles include a binder and an electrically conductive polymer and are stabilized by a nonionic stabilizer. The dispersant is obtained by polymerizing monomers into an electrically conductive polymer in the presence of a dispersant in a binder stabilized with a nonionic stabilizer. Under the given conditions, the nonionic stabilizer is not filled. The nonionic stabilizer can be selected within a wide range and can be added (chemically bonded) into the binder as well as physically adsorbed onto the binder particles (physically bound). The nonionic stabilizers include alkylamines, alkylamides, (ethoxylated) alkyl alcohols, alkyl pyrrolidones, (ethoxylated) alkyl phenols, polyoxyalkyl esters, polyoxyalkyl ethers, glycolalkyl ethers, glycerolalkyl ethers, fatty acid esters. , (Ethoxylated) sorbitan alkylate, (hydroxy (meth) ethyl cellulose, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide. Because of the high efficiency above, polyoxy Preference is given to using alkyl ethers, particularly suitable polyoxyalkyl ethers, for example polyoxyethylene ethers such as polyethylene glycol, alkoxypolyethylene glycols such as methoxypolyethylene glycol and ethylene oxide / propylene oxide copolymers. In other cases, polyoxyalkyl esters are preferred because of their low toxicity. An overview of stabilizers is described in Helmut Stache and Kurt Kosswig's Tensid-Taschenbuch, Carl Hanser Verlag Wien, 1990.
    If desired, the dispersing agent of the binder particles will also include small amounts of stabilizers, cationic stabilizers and / or anionic stabilizers comprising both nonionic and ionic moieties. The nonionic moiety preferably comprises at least 10 carbon atoms. Widely used anion stabilizers include alkyl sulfates and alkyl sulfonates, ethoxylated alkyl sulfates, sulfonates and phosphates, ethoxylated alkylcarboxylic acids and alkylphenol carboxylic acids, ethoxylated alkyl phenol sulfates and sulfonates, sulfosuccinates And carboxylates. Widely used cationic stabilizers are primary, secondary, tertiary and quaternary ammonium salts, alkylpyridinium salts and acetyl polyamines.
    Suitable nonionic stabilizers usually have a weight average molecular weight between 100 and 1,000,000, preferably between 500 and 5,000. Polymeric nonionic stabilizers suitable for the present invention consist of monomeric units having 1-50 carbon atoms, preferably 1-20 carbon atoms. Optionally, the polymerizable nonionic stabilizer consists of several units having different numbers of carbon atoms. Examples of such stabilizers are ethylene oxide / propylene oxide copolymers. The nonionic stabilizer can be added to the dispersant of the binder particles by conventional methods.
    It is preferred that a nonionic stabilizer can be chemically bound to the binder used. This can be done by adding a nonionic stabilizer in the binder by adding a nonionic stabilizer during the polymerization of the binder. It is possible to graft nonionic stabilizers on already polymerized binders. Usually the dispersant of the binder particles contains 1 to 35% by weight, preferably 5 to 25% by weight of the nonionic stabilizer relative to the total weight of the binder and stabilizer.
    The binder used in the dispersant according to the invention is preferably a known non-doping polymer with good coatability. The polymers include alkyd resins, polyester resins, amino resins, phenolic resins, polyurethane resins, epoxy resins, acrylate resins, cyclic rubbers, polyisoprene, rubbers such as natural rubber, silicone resins, poly (vinyl chloride), Poly (vinyl ester), for example poly (vinyl acetate), polyolefins comprising units selected from the group of ethene, propene, butadiene and styrene, hydrocarbon resins such as (co) polymers of cyclopentadiene.
    Alkyd resins that can be used as binders in the dispersants are in the group consisting of glycerol, pentaerythritol, ethylene glycol, sorbitol, trimethylol ethane, trimethylol propane, dipentaerythritol, tripentaerythritol, neopentyl glycol and diethylene glycol Polyols selected and polycarboxylic acids or derivatives thereof selected from the group consisting of phthalic anhydride, phthalic acid, isophthalic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, and fatty acids such as linoleic acid and oleic acid. Methods of making alkyd resins are known to those of ordinary skill in the art and described in H.F. Mark et al. Encyclopedia of Chemical Technology, 1978, vol. 2, pp. Described in 18-50.
    Suitable polyester resins include dicarboxylic acid units or derivatives thereof selected from the group consisting of maleic anhydride, fumaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and tetrachlorophthalic acid, and 1,2-propanol, It consists of diol units selected from the group consisting of 1,3-butanol, ethylene glycol, neopentyl glycol, diethylene glycol, bisphenol-A and tricyclodecane dimethanol. Optionally monofunctional and / or trifunctional monomer units can also be used. Possible methods of making polyester resins are known to those of ordinary skill in the art and include Oil and Color Chemists' Association, Australia in "Surface coatings, vol. 1-Raw materials and their usage", Chapman and Hall Ltd, 1983, pp. 78-87.
    Suitable epoxy resins are derived, for example, from bisphenol A and epichlorohydrin. As epoxidized aliphatic and cycloaliphatic dienes, for example 3,4-epoxycyclo-hexylmethyl-3,4-epoxycyclohexane carboxylate and 4-epoxyethyl-1,2-epoxycyclohexane can also be used. Possible methods of preparing epoxy resins are known to those of ordinary skill in the art and described in Ullman's Encyclopedia of Industrial Chemistry, 1985, vol. A9, pp. 547-563.
    Suitable polyurethane resins are reaction products of isocyanates and polyols. The isocyanate is 1,6-hexamethylene diisocyanate, polymethylene polyphenylisocyanate, 4,4'-methylene bis- (phenylisocyanate), 1,5-naphthalene diisocyanate, bitolylene diisocyanate, methylene-bis (cyclohexyl Isocyanate), isophorone diisocyanate, trimethylhexamethylene diisocyanate, m-xylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane It is selected from the group consisting of. The polyol is selected from the group consisting of polyether polyols and polyester polyols. Possible methods of preparing polyurethane resins are described in Kirk Othmer's Encyclopedia of Chemical Technology, 1982, vol. 23, pp.576-608.
    Dispersing agent of polyurethane resin is J.W. Rosthauser et al., Advances in Urethane Science and Technology, 1987, Stanford, vol. 10, pp. 121-162 and D. Dieterich in progress in Organic Coatings, 1981, vol. 9, pp. It can be stabilized by adding polyoxyethylene flakes on a polyurethane chain as described in 291-332. The pieces may consist of modified diol or isocyanate units, but can add the monohydroxy functional polyoxyethylene polyether directly on the polyurethane chain.
    Suitable amino resins are reaction products of formaldehyde with compounds containing amino groups such as melamine, benzoguanamine, glycoluril and urea. Amino resins and methods of making them are described in Oil and Color Chemists' Association, Australia in "Surface coatings, vol. 1-Raw materials and their usage", Chapman and Hall Ltd, 1983, pp. 87-98.
    Suitable phenolic resins are reaction products of phenolic compounds and aldehyde compounds, or derivatives thereof. The phenolic compound is selected from the group consisting of phenol, o-cresol, 2,4-xylenol, bisphenol-A, p-phenylphenol and p-t-butylphenol. The aldehyde compound is formaldehyde. Phenolic resins and methods of making them are described in Oil and Color Chemists' Association, Australia in "Surface coatings, vol. 1-Raw materials and their usage", Chapman and Hall Ltd, 1983, pp. 99-104.
    Suitable silicone resins are the hydrolysis products of di- and trifunctional chlorosilanes. In order to obtain the above, chlorosilane is dissolved in an organic solvent such as toluene or xylene and hydrolyzed with water. Silicone resins can also be prepared by treating and polymerizing alkoxysilanes such as methoxy, ethoxy and / or propoxy silanes with a strong acid in an aqueous medium. Silicone resins and methods of making them are described in Oil and Color Chemists' Association, Australia in "Surface coatings, vol. 1-Raw materials and their usage", Chapman and Hall Ltd, 1983, pp. 134-143.
    Suitable acrylate resins include homopolymerization of (meth) acrylate monomers such as methyl methacrylate, ethyl methacrylate or ethyl acrylate, or aliphatic with acrylonitrile, methacrylamide, maleic anhydride, terminal acrylate groups It can be obtained by copolymerization with monomers reacted with chain, methacrylic acid, vinyl acetate or styrene. Acrylate resins and methods of making them are described in Oil and Color Chemists' Association, Australia in "Surface coatings, vol. 1-Raw materials and their usage", Chapman and Hall Ltd, 1983, pp. 144-157.
    Optionally, a mixture of several of the binders mentioned above is used in the dispersant. It is also possible to use hybrid systems. Preferably, polyurethane resins are used as binders in the compositions according to the invention.
    The binder in the dispersant may optionally be provided with a functional group. By reacting the functional group, the binder can be crosslinked or bonded onto the substrate during curing of the composition according to the invention. Such functional groups include compounds having OH, NH 2 , NCO, epoxy, N-methylal, phosphate, sulfate and / or carboxylate functional groups or ethylenically unsaturated groups.
    The dispersant of the binder particles has a weight average particle size between 10 nm and 10 μm, preferably between 10 nm and 3 μm. The solids content of the dispersant of the binder particles is usually from 1 to 90 wt%.
    The invention also relates to a process for the preparation of the composition according to the invention. The manufacturing method of the dispersing agent of an electrically conductive particle is performed as follows. Monomers that may be made of an electrically conductive polymer may be polymerized into an electrically conductive polymer in the dispersant of the binder particles in the dispersant and include a nonionic stabilizer. Optionally a polymerization catalyst is also added. The order of adding the various components to the dispersant of the binder particles is not critical to the construction of the present invention. In the presence of a polymerization catalyst, the monomer units are polymerized to form an electrically conductive polymer. In this process, the monomers can polymerize in the dispersant to form oligomers or electrically conductive polymers, and relatively less soluble oligomers or electrically conductive polymers in the dispersant precipitate on the stabilized binder particles. This leads to a dispersant of electrically conductive particles comprising the electrically conductive polymer and is mainly adsorbed at the surface of the binder particles. Dispersants of the electrically conductive particles may also include free electrically conductive polymers.
    The temperature at which the dispersant of the electrically conductive particles is prepared is usually between -50 and 200 ° C, preferably between -10 and 80 ° C. The preparation time usually varies from seconds to days depending on the rate of polymerization of the monomer units for the electrically conductive polymer.
    The polymerization, optionally added to the dispersant of the binder particles, includes inorganic acids such as hydrochloric acid, sulfuric acid, chlorosulfonic acid and nitric acid, iron, aluminum, tin, titanium, zirconium, chromium, manganese, cobalt, copper, molybdenum, tungsten, ruthenium, Lewis acids, which are compounds containing cations such as nickel, palladium and / or platinum, and those skilled in the art from groups such as halogens, sulfates, nitrates, aryl sulfonates and / or acetyl acetonates Is selected. Other suitable catalysts are organic catalysts such as ozone, diazonium salts, benzoquinones and antaquinones. In certain polymerization reactions, Ziegler-Natta catalysts and K 2 Cr 2 O 7 , K 2 S 2 O 8 , Na 2 S 2 O 8 , NaBO 3 , H 2 O 2 , NOBF 4 , NO 2 BF 4 , NO 2 PF 6 , NOClO 4 , NOAsF 6 , NOPF 6 and (NH 4 ) 2 S 2 O 8 are valid. Valid catalysts include FeCl 3 , FeBr 3 , FeCl 3 · 6H 2 O, CuSO 4 , Fe (NO 3 ) 3 · 9H 2 O, CuCl 2 · 2H 2 O, K 3 Fe (CN) 6 , Cu (NO 3 ) 2 , Fe (BF 4 ) 3 , Fe (ClO 4 ) 3 · 9H 2 O, Fe 2 (SO 4 ) 3 · 5H 2 O, Fe 2 (SiF 6 ) 3 , Cu (ClO 4 ) 2 , Cu ( BF 4 ) 2 , CuSiF 6 , RuCl 3 , MoCl 5 , WCl 6 and (C 5 H 5 ) 2 Fe + FeCl 4 − . Optionally a mixture of several catalysts is used. Iron (III) chloride is preferred as a catalyst for the production of polypyrrole.
    Quantification of the added catalyst has a catalyst: monomer molar ratio between 1:10 and 10: 1, preferably between 1: 3 and 3: 1.
    The monomer unit consisting of the electrically conductive polymer in the composition according to the invention is preferably selected from the group consisting of pyrrole, thiophene, indole, carbazole, furan, benzene, aniline, acetylene and derivatives of said monomers. At the stability and level of conductivity, electrically conductive polymers consisting of pyrrole, thiophene or aniline units or derivatives of such monomers are preferred.
    Examples of the monomer derivatives include N-methylpyrrole, N-ethylpyrrole, Nn-propylpyrrole, Nn-butylpyrrole, N-phenylpyrrole, N-tolylpyrrole, N-naphthylpyrrole, 3-methylpyrrole, 3,4 -Dimethylpyrrole, 3-ethylpyrrole, 3-n-propylpyrrole, 3-n-butylpyrrole, 3-phenylpyrrole, 3-tolylpyrrole, 3-naphthylpyrrole, 3-methoxypyrrole, 3,4-di Methoxypyrrole, 3-ethoxypyrrole, 3-n-propoxypyrrole, 3-phenoxypyrrole, 3-methyl-N-methylpyrrole, 3-methoxy-N-methylpyrrole, 3-chloropyrrole, 3- Bromopyrrole, 3-methylthiopyrrole, 3-methylthio-n-methylpyrrole, 2,2'-bithiophene, 3-methyl-2,2'-bithiophene, 3,3'-dimethyl-2, 2'-bithiophene, 3,4-dimethyl-2,2'-bithiophene, 3,4-dimethyl-3 ', 4'-dimethyl-2,2'-bithiophene, 3-methoxy-2,2 '-Bithiophene, 3,3'-dimethoxy-2,2'-bithiophene, 2,2', 5,2 "-terthiophene, 3-methyl-2,2 ', 5', 2"- Terthiophene, 3,3'-dimethyl-2,2 ', 5', 2 "-terthiophene, 2-cyclohexylaniline, aniline, 4-propanoylaniline, 2- (methylamino) aniline, 2 -(Dime Amine) aniline, o-toluidine, 4-carboxaniline, n-methylaniline, m-hexylaniline, 2-methyl-4-methoxy-carbonylaniline, n-propylaniline, n-hexylaniline, m-toluidine, o-ethylaniline, m-ethylaniline, o-ethoxyaniline, m-butylaniline, 5-chloro-2-ethoxy-aniline, m-octylaniline, 4-bromoaniline, 2-bromoaniline, 3 Bromoaniline, 3-acetamidoaniline, 4-acetamidoaniline, 5-chloro-2-methoxy-aniline, 2-acetylaniline, 2,5-dimethylaniline, 2,3-dimethylaniline, N , N-dimethylaniline, 4-benzylaniline, 4-aminoaniline, 2-methylthiomethylaniline, 4- (2,4-dimethyl-phenyl) aniline, 2-ethylthioaniline, n-methyl-2,4- Dimethylaniline, n-propyl-m-toluidine, n-methyl-o-cyanoaniline, 2,5-dibutylaniline, 2,5-dimethoxyaniline, o-cyanoaniline, tetrahydronaphthylamine, 3 -(n-butane sulfonic acid) aniline, 2-thiomethylaniline, 2,5-dichloroa Lean, 2,4-dimethoxyaniline, 3-propoxymethylaniline, 4-mercaptoaniline, 4-methylthioaniline, 3-phenoxyaniline, 4-phenoxyaniline, n-hexyl-m-toluidine, 4 -Phenylthioaniline, n-octyl-m-toluidine, tetrahydrobenzo [c] thiophene, 4-trimethylsilylaniline and 3,4- (alkyline-vic-dioxy-) thiophene.
    Optionally the electrically conductive polymer consists of a mixture of several monomer units mentioned above.
    In certain embodiments, the monomers mentioned above may be obtained by deblocking the precursor monomers in situ. Promonomers are molecules that cannot be polymerized as described above. However, in a simple conversion step, the molecule is transformed into polymerizable monomer units. The converting step consists in removing blocking groups that block one or more reactive sites. Another possibility is to raise the oxidation level of the molecule to remove the electron-withdrawing groups and to prevent polymerization. In another embodiment, intramolecular reactions occur, such as the Diels-Alder back reaction, and the promonomers are converted to polymerizable monomer units. After activation, an electrically conductive polymer may be formed and certain promonomers may be used that result in polymerizable monomer units.
    Suitable precursor molecules are molecules having the structure of formula (3):
    In Formula 3, X is , -S- or -O-;
    R 1 is hydrogen, —C (O) OH, —C (O) C (O) OH, —C (O) H, —SO 3 H, —I or —Br;
    R 2 is hydrogen, an alkyl group (with 1-10 carbon atoms), —C (O) OH or halogen;
    R 3 is hydrogen, an alkyl group (with 1-10 carbon atoms), —C (O) OH or halogen;
    R 4 is hydrogen, —C (O) OH, —C (O) C (O) OH, —C (O) H, —SO 3 H, —I or —Br;
    R 5 is hydrogen or an alkyl, aryl, alkoxy or silyl group;
    R 1 -R 4 may not all be hydrogen at the same time, and R 2 and R 3 may both form a closed ring structure. Preferably, pyrrole-2-carboxylic acid is used. Synthesis of the promonomer is described in J. Am. Pharm. Assoc. 45, 509 (1956).
    All combinations of X, R 1 , R 2 , R 3 and R 4 are possible. R 1 and R 4 groups can be removed thermally or photochemically and include the formation of substituted or unsubstituted pyrrole, thiophene or furan monomers on the R 2 and / or R 3 moieties. The promonomer can be deblocked and freely polymerized via the R 1 and R 4 positions. R 2 and R 3 groups may be the same or different. In addition, both R 2 and R 3 groups may form closed ring structure moieties. Suitable examples of such promonomers are 3,4- (alkylene-vic-dioxy-) thiophene-2,5-dicarboxylic acid.
    Another suitable precursor monomer from which the electrically conductive polymer can be prepared is a precursor monomer having a structure according to formula (4):
    X 1 and X 2 are the same or different, , -S- or -O-;
    R 1 and R 2 are the same or different and are hydrogen or an alkyl group having 1-10 carbon atoms;
    R 4 is hydrogen or an alkyl, aryl or alkoxy group.
    The precursor monomer according to Chemical Formula 4 is J. Chem. Soc. Perkin Trans. I (1985), pp. Can be synthesized as described in 1277-1284. Another suitable promonomer is 4-aminobenzoic acid (see P. Ruelle, 7. Chem. Soc. Perkin trans. II, 1953 (1986)). 3,4-disubstituted thiophenes can also be used (see US Pat. No. 4,987,042). Combinations of all kinds of promonomers are possible. If desired, precursor oligomers may also be used. The promonomer may be activated by thermal or photochemical treatment.
    The weight ratio between the electrically conductive polymer and the binder varies within a wide range depending on the desired electrical conductivity and coatability. The ratio is usually between 0.1: 99.9 and 80:20, preferably between 0.1: 99.9 and 20:80, in particular between 0.1: 99.9 and 10:90.
    Depending on the electrically conductive polymer obtained, the electrical conductivity can be improved by a doping step (oxidation or reduction) using known doping techniques and reagents. This is mentioned in 'Handbook of conducting polymers' (T.A. Skotheim, Marcel Dekker Inc., New York, USA (1986)). Doping is carried out by adding the doping agent to the dispersant of the electrically conductive particles.
    The electrically conductive composition according to the present invention is prepared by mixing the dispersant of the electrically conductive particles with the radiation curable resin.
    Optionally, less than 60 wt% of fillers and / or antioxidants may additionally be added to the electrically conductive composition. Examples of fillers that may be added are talc, barium sulfate, calcium carbonate, fiber, pigments (brightly-adsorbed) such as titanium white, colored pigments such as iron oxide and SiO 2 , kaolin, wollastonite and glass. In addition, adhesion promoters, flow promoters, fillers, thickeners, surface improvers, antifoams, preservatives, curing agents, desiccants, conductive materials such as carbon black, conductive fibers and conductive flakes, stabilizers and binders.
    The dispersant selected is one in which the first binder and the electrically conductive polymer are insoluble or hardly soluble in the dispersant. However, monomeric units and catalysts consisting of electrically conductive polymers are dissolved in the dispersant. The dispersants include water, aromatic compounds such as benzene, toluene and xylene, alcohols such as methanol and ethanol, hydrocarbons such as pentane and hexane, ethers such as dioxane, diethyl ether, ethylmethyl ether and tetrahydrofuran, acetone, di Ketones such as ethyl ketone and methyl ethyl ketone, halogenated compounds such as CHCl 3 , CH 2 Cl 2 and carbon tetrachloride, esters such as ethyl formiate and ethyl acetate, acetonitrile, nitromethane, dimethyl sulfoxide, dimethyl formamide, tri It is selected from the group consisting of compounds such as ethyl phosphate, dimethyl acetamide and pyridine. Mixtures of several dispersants may also be used.
    The dispersant may not only disperse the electrically conductive particles, but also preferably dissolve and disperse the resin. For environmental reasons, it is preferable to use water as a dispersant.
    The invention also relates to the use of the composition according to the invention for use as a conductive coating.
    The present invention also relates to a coating material produced in whole or in part using the composition according to the invention, and to a substrate coated in whole or in part with said coating material.
    The invention is further illustrated by the following examples and comparative experiments, but is not limited thereto.
    The surface resistivity of the coated product was H.H. Measurements are made in the methods described in Wieder in Laboratory Notes on Electrical and Galvanomagnetic Measurements, Elsevier, New York, 1979.
    Turbidity is measured according to ASTM D 1003.
    Example 1
    A mixture of 13.6 g of dispersant (ConQuest R XP 1000 in DSM) and 2 g of UV curable resin (Uraflex R XP 405UV in DSM resin) of electrically conductive particles in 38.8 g of water is stored over night.
    A dispersant of electrically conductive particles is prepared as follows: 12.32 g of Fe (NO 3 ) 3 .9H 2 O is dissolved in 234.2 g of demineralized water (solution A). 0.89 g of pyrrole is dissolved in 43.6 g of water (solution B). The two solutions are added to 20 g of a 40 wt% polyurethane dispersion in water and stabilized by adding methoxy polyethylene glycol chains (Mw = 750 g / mol). The dispersant is centrifuged at 14,000 rpm for 1 hour to redisperse the precipitate with 20 wt% dispersant in water.
    A 20 μm thick layer of the mixture stored over night is added to the glass plate. After the water has evaporated at 50 ° C. for 15 minutes, the resin is cured to a radiation dose of 4 J / cm 2. The conductive film thus obtained has a surface resistivity of 10 6 Ohm / And a haze of 0.5%.
    Comparative Experiment A
    In Examples 1, solutions A and B are mixed and centrifuged, 0.68 g of precipitate is dispersed in 52.4 g of water. To this is added 2 g of Uraflex XP 405UV. The film produced using the dispersant is 10 12 Ohm / The above has a surface resistivity and a haze of 8%.
    权利要求:
    Claims (11)
    [1" claim-type="Currently amended] An electrically conductive composition comprising a dispersant of electrically conductive particles in a dispersant and a radiation curable resin,
    The dispersing agent of the electrically conductive particles comprises a binder and an electrically conductive polymer, characterized in that stabilized by a nonionic stabilizer.
    [2" claim-type="Currently amended] The method of claim 1,
    The radiation curable resin may or may not be combined with (a) a compound having an ethylenically unsaturated group on an electron-withdrawing group, a compound consisting of an ethylenically unsaturated group on an electron-donating group (b), or an electron-coating A composition comprising a component such as an allyl group-containing compound (c) or a mixture of compounds (b) and (c) on a female group.
    [3" claim-type="Currently amended] The method of claim 2,
    The radiation curable resin includes the entire compound (a) having an ethylenically unsaturated group on the electron-withdrawing group, or a compound (b) having 50 mol% of the compound (a) and an ethylenically unsaturated group on the electron-donating group 50 mol% of a mixture or an allyl group-containing compound (c) or a mixture of (b) and (c).
    [4" claim-type="Currently amended] The method of claim 2 or 3,
    The compound (a) is characterized in that it comprises an acrylate, methacrylate, malate, fumarate, itaconate, citraconate or mesaconate groups.
    [5" claim-type="Currently amended] The method according to any one of claims 2 to 4,
    The compound (b) is a composition, characterized in that the vinyl ether, vinyl ester, vinyl amide, vinylamine, vinyl thioether or vinyl thioester.
    [6" claim-type="Currently amended] The method according to any one of claims 2 to 5,
    The compound (c) is an allyl ether, allyl ester, allyl alcohol, allyl amine or aryl amide.
    [7" claim-type="Currently amended] The method according to any one of claims 1 to 6,
    The binder is a composition, characterized in that the polyurethane resin.
    [8" claim-type="Currently amended] In the method for producing the electrically conductive composition according to any one of claims 1 to 7, by mixing a dispersant of the electrically conductive particles and the radiation curable resin,
    The dispersant of the electrically conductive particles can be obtained by polymerizing a monomer into an electrically conductive polymer in the dispersant of the binder particles in the dispersant containing a nonionic stabilizer.
    [9" claim-type="Currently amended] Use of an electrically conductive composition, characterized in that the electrically conductive composition according to claim 1 is used as a conductive coating.
    [10" claim-type="Currently amended] A coating material, which is prepared in whole or in part using the electrically conductive composition according to any one of claims 1 to 7.
    [11" claim-type="Currently amended] Substrate, characterized in that it is coated in whole or in part with the coating material according to claim 10.
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    同族专利:
    公开号 | 公开日
    CA2277762A1|1998-07-23|
    EP0953020A1|1999-11-03|
    JP2001508490A|2001-06-26|
    NL1005007C2|1998-07-16|
    TW434289B|2001-05-16|
    WO1998031754A1|1998-07-23|
    AU5499398A|1998-08-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-01-15|Priority to NL1005007
    1997-01-15|Priority to NL1005007A
    1998-01-07|Application filed by 윌리암 로엘프 드 보에르, 디에스엠 엔.브이
    2000-11-25|Publication of KR20000070078A
    优先权:
    申请号 | 申请日 | 专利标题
    NL1005007|1997-01-15|
    NL1005007A|NL1005007C2|1997-01-15|1997-01-15|Radiation-curing conductive coating dispersion, method of preparation and coatings manufactured therewith.|
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